EP1559705A1 - Process for production of hydroxybenzoic acids - Google Patents
Process for production of hydroxybenzoic acids Download PDFInfo
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- EP1559705A1 EP1559705A1 EP03799169A EP03799169A EP1559705A1 EP 1559705 A1 EP1559705 A1 EP 1559705A1 EP 03799169 A EP03799169 A EP 03799169A EP 03799169 A EP03799169 A EP 03799169A EP 1559705 A1 EP1559705 A1 EP 1559705A1
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- Prior art keywords
- compound
- alkaline metal
- tert
- phenol
- hydroxybenzoic acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/64—Preparation of O-metal compounds with O-metal group bound to a carbon atom belonging to a six-membered aromatic ring
- C07C37/66—Preparation of O-metal compounds with O-metal group bound to a carbon atom belonging to a six-membered aromatic ring by conversion of hydroxy groups to O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/15—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction of organic compounds with carbon dioxide, e.g. Kolbe-Schmitt synthesis
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C65/00—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C65/01—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups
- C07C65/03—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups monocyclic and having all hydroxy or O-metal groups bound to the ring
Definitions
- the present invention relates to a method for preparing a hydroxybenzoic acid compound.
- a solid-gas phase reaction to react phenol potassium with carbon dioxide which is known as Kolbe-Schmitt reaction
- the Kolbe-Schmitt reaction has some problems such as the long reaction time which is required due to the solid-gas phase reaction, the great loss of the reaction material because of side reaction due to the thermal non-uniformity of the reaction and the fluctuate of the yield because of the difficulty in controlling the reaction.
- liquid-phase methods wherein the reaction is conducted in a solvent or as slurry are proposed from the industrial viewpoints.
- Japanese Patent Application Laid Open No. 3-90047 discloses a method for preparing 3,5-dialkyl salicylic acid comprising heating 2,4-dialkylphenol and alkaline metal hydroxide in a mixed solvent of hydrocarbon and 1,3-dimethyl-2-imidazolidinone to give anhydrous 2,4-dialkylphenol alkaline metal salt through azeotropic dehydration and reacting said metal salt with carbon dioxide in said mixed solvent to give 3,5-dialkyl salicylic acid.
- the aqueous solution of 3,5-dialkyl salicylic acid alkaline metal salt obtained by the reaction contains a large amount of aprotic polar organic solvent, the expensive aprotic polar organic solvent is difficult to collect because it transfers into the filtrate after the acid precipitation method.
- Japanese Patent Application Laid Open No. 10-231271 proposes a method for preparing a hydroxybenzoic acid compound wherein an aprotic polar organic solvent is used as reaction solvent for the reaction between a phenol compound and an alkaline metal compound, characterized in that the molar ratio of the phenol compound to the total amount of the alkaline metal compound and the aprotic polar organic solvent is larger than 1.
- the yield of hydroxybenzoic acid obtained by said method which uses an excess amount of the phenol compound over the total amount of the alkaline metal compound and the aprotic polar solvent, is not sufficient.
- side product such as a dimer of the phenol compound produced during the Kolbe-Schmitt reaction in the presence of an aprotic polar organic solvent and therefore, it is difficult to obtain high-purity hydroxybenzoic acids.
- An object of the present invention is providing a method for preparing a hydroxybenzoic acid compound with high yield without using an expensive aprotic polar organic solvent.
- the present invention provides a method for producing a hydroxybenzoic acid compound comprising, dehydrating a phenol compound and an alkaline metal compound to form an alkaline metal salt of phenol and reacting the alkaline metal salt and carbon dioxide, wherein the dehydrating step is conducted by reacting said alkaline metal compound with an excess amount of the phenol compound, which is in excess of the alkaline metal compound, at a temperature of 160°C or above.
- the dehydration between the phenol compound and the alkaline metal compound is promoted and consequently, the alkaline metal salt of the phenol compound can be obtained with high yield and the remaining phenol can be used again as a solvent.
- "excess" amount of the phenol compound means that the amount of the phenol compound is two or more molar parts per 1 molar part of the alkaline metal compound.
- the amount of the phenol compound is preferably 2-30 molar parts, more preferably 3-15 molar parts and even more preferably 4-10 molar parts per 1 molar part of the alkaline metal compound.
- the alkaline metal salt of the phenol compound will precipitate and interfere with homogeneous stirring. Using more than 30 molar parts of phenol is permissible, but it will not bring about better result than using less amount of phenol and therefore, it is not economical.
- dehydrating of the alkaline metal compound and the phenol compound is conducted at a temperature of 160°C or above and preferably at 180-300°C. If the temperature during dehydration is lower than 160°C, the alkaline metal salt hardly be formed and water produced by the dehydration of the phenol and the alkaline metal compound can not be sufficiently removed. On the contrary, if the temperature during the dehydration step is higher than 300°C which is above the boiling point of the phenol, the phenol might be distilled out of the reaction system and the alkaline metal salt of phenol might be thermally decomposed due to such a high temperature.
- the phenol compound preferably used as a starting material is represented by formula (I): wherein, R is selected from the group consisting of hydrogen atom, linear or branched chain C1-20 alkyl, C1-20 alkenyl and C1-20 alkoxy groups; n is an integer from 1 to 4.
- alkyl substituted phenols preferably dialkyl substituted phenols are suitably used for the method of the present invention because of their high reaction selectivity and high reaction yield.
- alkyl groups suitable for the substituents are methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, n-octyl and tert-octyl.
- alkyl substituted phenols preferably used in the present invention are o-cresol, p-cresol, m-cresol, 2,6-dimethylphenol, 3,5-dimethylphenol, 2,5-dimethylphenol, o-isopropylphenol, 2,6-di-tert-butylphenol, 2,4-di-tert-butylphenol, 2,5-di-tert-butylphenol, 4-n-octylphenol and 4-tert-octylphenol.
- substituents on the phenol may be the same or different.
- a preferable alkaline metal compound used in the present invention is sodium hydroxide or potassium hydroxide.
- sodium hydroxide is preferable because it allows rapid dehydration and is inexpensive.
- water produced during the dehydrating step is preferably removed from the reaction system.
- an azeotropic dehydration agent may be added to the reaction mixture.
- hydrocarbon type solvents which are selected from the group consisting of aliphatic hydrocarbons such as octane, nonane, decane, undecane, dodecane, ligroin and kerosene; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, ethylbenzene, cumene, diphenylether and naphthalene; and halogenated hydrocarbons such as chlorobenzene, o-dichlorobenzene, and p-dichlorobenzene are used as an azeotropic dehydration agent.
- the amount of the azeotropic dehydration agent used in the reaction may vary depending on the amount of water contained in the reaction system, and in general, the amount of the azeotropic dehydration agent used may be 2-10 parts by weight per 1 part by weight of water contained in the system.
- the liquid state substituted phenol acts as solvent and therefore, it is not necessary to add any other solvent in the step to obtain an alkaline metal salt of the phenol compound.
- an additional solvent other than the substituted phenol is also included in the scope of the present invention.
- Solvents other than the phenol compound used in the dehydrating step may be any of those other than aprotic polar organic solvents.
- solvents examples include light oil, kerosene, petrol, lubrication oil, white oil, alkylbenzene, alkylnaphthalene, diphenyl, diphenylalkane, alkyldiphenyl, triphenyl, hydrogenated triphenyl, diphenylether, alkylphenylether, alkyldiphenylether, high boiling point higher alcohols such as iso-octyl alcohol and a mixture thereof.
- dehydrating step is carried out under inert gases atmosphere such as nitrogen, helium and argon gas.
- the alkaline metal salt of the phenol compound obtained by the dehydrating step is subjected to the next step, i.e. reacting the same with carbon dioxide.
- the reaction of the alkaline metal salt of the phenol compound and carbon dioxide is curried out in an autoclave under the carbon dioxide pressure of preferably 2.0-10 kgf/cm 2 (G), more preferably 4.0-8.0 kgf/cm 2 (G) at a reaction temperature preferably of 160-300°C, and more preferably of 170-290°C.
- the reaction time may vary depending on the carbon dioxide pressure and the reaction temperature, and in general, it may be 1-6 hrs, and preferably 1-4 hrs.
- reaction mixture comprising the alkaline metal salt of the hydroxybenzoic acid compound
- water is added and then the mixture is separated into the solvent and water phases.
- the water phase i.e. an aqueous solution containing the alkaline metal salt of the hydroxybenzoic acid compound is added with an acid to precipitate the hydroxybenzoic acid compound.
- the precipitates may be collected by filtration and centrifugation to give crystalline hydroxybenzoic acid compound.
- the solvent phase separated from the reaction mixture in this example is mainly consisting of the starting phenol compound and therefore, the solvent phase may be used again as starting phenol compound directly or, if necessary, after purified by, such as, filtration, distillation or carbon treatment.
- Non limiting examples of the hydroxybenzoic acid compounds produced by the method of the present invention are 3,5-di-tert-butyl-4-hydroxybenzoic acid, 3,5-di-tert-butyl-2-hydroxybenzoic acid, 3-methyl-4-hydroxybenzoic acid, 2,6-dimethyl-4-hydroxybenzoic acid, 2-ethyl-4-hydroxybenzoic acid and 3,5-diethyl-4-hydroxybenzoic acid.
- 3,5-di-tert-butyl-4-hydroxybenzoic acid produced from 2,6-di-tert-butylphenol and 3,5-di-tert-butyl-2-hydroxybenzoic acid 2,4-di-tert-butylphenol are preferable because they are obtained with high yields.
- the method of the present invention highly pure hydroxybenzoic acid compound can be obtained with low amount of side-products and with high yields. Moreover, the method of the present invention makes it possible to produce the hydroxybenzoic acid compound at low cost with simple steps without using an expensive aprotic polar solvent. Furthermore, the solvent phase separated from the reaction mixture in the method contains little amount of by-products and therefore, it can be used again as the starting phenol compound.
- the hydroxybenzoic acid compound produced by the method of the present invention can be used as a raw material for producing ultraviolet absorber, antioxidant and the like which are contained in plastics such as polypropylene.
- Example 2 By the same method as Example 1 except that dehydrating step was conducted at 180°C, 37.5 g of powder of 3,5-di-tert-butyl-4-hydroxybenzoic acid was obtained. The yield to the fed amount of sodium hydroxide was 50%.
- Example 2 The same method as Example 1 was carried out except that dehydrating step was conducted at 150°C. In the comparative example 1, no precipitation was generated by adding 73% aqueous sulfuric acid and 3,5-di-tert-butyl-4-hydroxybenzoic acid could not be obtained.
- Example 2 The same method as Example 1 was carried out except that 2,4-di-tert-butylphenol was used instead of 2,6-di-tert-butylphenol, 60g of powdery 3,5-di-tert-butyl-2-hydroxybenzoic acid was obtained. The yield to the fed amount of sodium hydroxide was 80%.
- the present invention provides a method for producing highly pure hydroxybenzoic acid compound with high yield and little side-products.
- the present invention makes it possible to produce hydroxybenzoic acid compound by simple steps at low cost without using expensive aprotic polar organic solvent.
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Abstract
The present invention provides a method for producing a hydroxybenzoic acid compound comprising, dehydrating a phenol compound and an alkaline metal compound to form the alkaline metal salt of the phenol compound and reacting the alkaline metal salt and carbon dioxide, wherein the dehydrating step is conducted by reacting the alkaline metal compound with an excess amount of the phenol compound at a temperature of 160 DEG C or above. According to the method of the present invention, the hydroxybenzoic acid compound can be obtained by simple steps with low cost without using an expensive aprotic polar organic solvent. The provided method can produce highly pure hydroxybenzoic acid compound comprising little by-products in high yield.
Description
The present invention relates to a method for
preparing a hydroxybenzoic acid compound.
As a method for preparing a hydroxybenzoic acid
compound, a solid-gas phase reaction to react phenol
potassium with carbon dioxide, which is known as Kolbe-Schmitt
reaction, has conventionally been used. The Kolbe-Schmitt
reaction, however, has some problems such as the
long reaction time which is required due to the solid-gas
phase reaction, the great loss of the reaction material
because of side reaction due to the thermal non-uniformity
of the reaction and the fluctuate of the yield because of
the difficulty in controlling the reaction. In recent
years, in order to overcome those problems of the solid-gas
phase Kolbe-Schmitt reaction, liquid-phase methods wherein
the reaction is conducted in a solvent or as slurry are
proposed from the industrial viewpoints.
For example, Japanese Patent Application Laid
Open No. 3-90047 discloses a method for preparing 3,5-dialkyl
salicylic acid comprising heating 2,4-dialkylphenol
and alkaline metal hydroxide in a mixed solvent of
hydrocarbon and 1,3-dimethyl-2-imidazolidinone to give
anhydrous 2,4-dialkylphenol alkaline metal salt through
azeotropic dehydration and reacting said metal salt with
carbon dioxide in said mixed solvent to give 3,5-dialkyl
salicylic acid.
Though the use of an aprotic polar organic
solvent such as 1,3-dimethyl-2-imidazolidinone in the
reaction makes it possible to attain a high reaction yield,
said method has some problems in collecting the product
from the reaction mixture and recovering the solvent. That
is, despite of the high reaction yield, 3,5-dialkyl
salicylic acid alkaline metal salt can not be sufficiently
collected by means of crystallization because of the high
solubility of the alkaline metal salt to the aprotic polar
organic solvent. In addition, though the aqueous solution
of 3,5-dialkyl salicylic acid alkaline metal salt obtained
by the reaction contains a large amount of aprotic polar
organic solvent, the expensive aprotic polar organic
solvent is difficult to collect because it transfers into
the filtrate after the acid precipitation method.
In order to solve the above problems, Japanese
Patent Application Laid Open No. 10-231271 proposes a
method for preparing a hydroxybenzoic acid compound wherein
an aprotic polar organic solvent is used as reaction
solvent for the reaction between a phenol compound and an
alkaline metal compound, characterized in that the molar
ratio of the phenol compound to the total amount of the
alkaline metal compound and the aprotic polar organic
solvent is larger than 1.
However, the yield of hydroxybenzoic acid
obtained by said method, which uses an excess amount of the
phenol compound over the total amount of the alkaline metal
compound and the aprotic polar solvent, is not sufficient.
There is also a problem of side product such as a dimer of
the phenol compound produced during the Kolbe-Schmitt
reaction in the presence of an aprotic polar organic
solvent and therefore, it is difficult to obtain high-purity
hydroxybenzoic acids.
Furthermore, use of expensive aprotic polar
organic solvent results in high cost.
An object of the present invention is providing a
method for preparing a hydroxybenzoic acid compound with
high yield without using an expensive aprotic polar organic
solvent.
The present invention provides a method for
producing a hydroxybenzoic acid compound comprising,
dehydrating a phenol compound and an alkaline metal
compound to form an alkaline metal salt of phenol and
reacting the alkaline metal salt and carbon dioxide,
wherein the dehydrating step is conducted by reacting said
alkaline metal compound with an excess amount of the phenol
compound, which is in excess of the alkaline metal compound,
at a temperature of 160°C or above.
According to the method of the present invention,
by using an excess amount of the phenol compound over the
alkaline metal compound, the dehydration between the phenol
compound and the alkaline metal compound is promoted and
consequently, the alkaline metal salt of the phenol
compound can be obtained with high yield and the remaining
phenol can be used again as a solvent.
In the present specification and claims, "excess"
amount of the phenol compound means that the amount of the
phenol compound is two or more molar parts per 1 molar part
of the alkaline metal compound. In the present invention,
the amount of the phenol compound is preferably 2-30 molar
parts, more preferably 3-15 molar parts and even more
preferably 4-10 molar parts per 1 molar part of the
alkaline metal compound. In case where the amount of the
phenol compound is less than 2 molar parts, the alkaline
metal salt of the phenol compound will precipitate and
interfere with homogeneous stirring. Using more than 30
molar parts of phenol is permissible, but it will not bring
about better result than using less amount of phenol and
therefore, it is not economical.
In the method of the present invention,
dehydrating of the alkaline metal compound and the phenol
compound is conducted at a temperature of 160°C or above
and preferably at 180-300°C. If the temperature during
dehydration is lower than 160°C, the alkaline metal salt
hardly be formed and water produced by the dehydration of
the phenol and the alkaline metal compound can not be
sufficiently removed. On the contrary, if the temperature
during the dehydration step is higher than 300°C which is
above the boiling point of the phenol, the phenol might be
distilled out of the reaction system and the alkaline metal
salt of phenol might be thermally decomposed due to such a
high temperature.
In the present invention, the phenol compound
preferably used as a starting material is represented by
formula (I):
wherein, R is selected from the group consisting of
hydrogen atom, linear or branched chain C1-20 alkyl, C1-20
alkenyl and C1-20 alkoxy groups; n is an integer from 1 to
4.
Among the above, alkyl substituted phenols (R=
alkyl group), preferably dialkyl substituted phenols are
suitably used for the method of the present invention
because of their high reaction selectivity and high
reaction yield. Examples of alkyl groups suitable for the
substituents are methyl, ethyl, n-propyl, iso-propyl, n-butyl,
sec-butyl, tert-butyl, n-octyl and tert-octyl.
Examples of alkyl substituted phenols preferably
used in the present invention are o-cresol, p-cresol, m-cresol,
2,6-dimethylphenol, 3,5-dimethylphenol, 2,5-dimethylphenol,
o-isopropylphenol, 2,6-di-tert-butylphenol,
2,4-di-tert-butylphenol, 2,5-di-tert-butylphenol, 4-n-octylphenol
and 4-tert-octylphenol.
In case there are two or more substituents on the
phenol, the substituents may be the same or different.
A preferable alkaline metal compound used in the
present invention is sodium hydroxide or potassium
hydroxide. In particular, sodium hydroxide is preferable
because it allows rapid dehydration and is inexpensive.
In the method of the present invention, water
produced during the dehydrating step is preferably removed
from the reaction system.
In order to promote the dehydrating step, an
azeotropic dehydration agent may be added to the reaction
mixture. In general, one or more of hydrocarbon type
solvents which are selected from the group consisting of
aliphatic hydrocarbons such as octane, nonane, decane,
undecane, dodecane, ligroin and kerosene; aromatic
hydrocarbons such as benzene, toluene, xylene, mesitylene,
ethylbenzene, cumene, diphenylether and naphthalene; and
halogenated hydrocarbons such as chlorobenzene, o-dichlorobenzene,
and p-dichlorobenzene are used as an
azeotropic dehydration agent. The amount of the azeotropic
dehydration agent used in the reaction may vary depending
on the amount of water contained in the reaction system,
and in general, the amount of the azeotropic dehydration
agent used may be 2-10 parts by weight per 1 part by weight
of water contained in the system.
In the method of the present invention, the
liquid state substituted phenol acts as solvent and
therefore, it is not necessary to add any other solvent in
the step to obtain an alkaline metal salt of the phenol
compound. However, the case where an additional solvent
other than the substituted phenol is used is also included
in the scope of the present invention. Solvents other than
the phenol compound used in the dehydrating step may be any
of those other than aprotic polar organic solvents.
Examples of such solvents are light oil, kerosene, petrol,
lubrication oil, white oil, alkylbenzene, alkylnaphthalene,
diphenyl, diphenylalkane, alkyldiphenyl, triphenyl,
hydrogenated triphenyl, diphenylether, alkylphenylether,
alkyldiphenylether, high boiling point higher alcohols such
as iso-octyl alcohol and a mixture thereof.
In the method of the present invention,
dehydrating step is carried out under inert gases
atmosphere such as nitrogen, helium and argon gas.
In the method of the present invention, the
alkaline metal salt of the phenol compound obtained by the
dehydrating step is subjected to the next step, i.e.
reacting the same with carbon dioxide.
The reaction of the alkaline metal salt of the
phenol compound and carbon dioxide is curried out in an
autoclave under the carbon dioxide pressure of preferably
2.0-10 kgf/cm2 (G), more preferably 4.0-8.0 kgf/cm2 (G) at
a reaction temperature preferably of 160-300°C, and more
preferably of 170-290°C. The reaction time may vary
depending on the carbon dioxide pressure and the reaction
temperature, and in general, it may be 1-6 hrs, and
preferably 1-4 hrs.
Into thus obtained reaction mixture comprising
the alkaline metal salt of the hydroxybenzoic acid compound,
water is added and then the mixture is separated into the
solvent and water phases. Next, the water phase, i.e. an
aqueous solution containing the alkaline metal salt of the
hydroxybenzoic acid compound is added with an acid to
precipitate the hydroxybenzoic acid compound. The
precipitates may be collected by filtration and
centrifugation to give crystalline hydroxybenzoic acid
compound.
The solvent phase separated from the reaction
mixture in this example is mainly consisting of the
starting phenol compound and therefore, the solvent phase
may be used again as starting phenol compound directly or,
if necessary, after purified by, such as, filtration,
distillation or carbon treatment.
Non limiting examples of the hydroxybenzoic acid
compounds produced by the method of the present invention
are 3,5-di-tert-butyl-4-hydroxybenzoic acid, 3,5-di-tert-butyl-2-hydroxybenzoic
acid, 3-methyl-4-hydroxybenzoic acid,
2,6-dimethyl-4-hydroxybenzoic acid, 2-ethyl-4-hydroxybenzoic
acid and 3,5-diethyl-4-hydroxybenzoic acid.
Among the above, 3,5-di-tert-butyl-4-hydroxybenzoic acid
produced from 2,6-di-tert-butylphenol and 3,5-di-tert-butyl-2-hydroxybenzoic
acid 2,4-di-tert-butylphenol are
preferable because they are obtained with high yields.
According to the method of the present invention,
highly pure hydroxybenzoic acid compound can be obtained
with low amount of side-products and with high yields.
Moreover, the method of the present invention makes it
possible to produce the hydroxybenzoic acid compound at low
cost with simple steps without using an expensive aprotic
polar solvent. Furthermore, the solvent phase separated
from the reaction mixture in the method contains little
amount of by-products and therefore, it can be used again
as the starting phenol compound.
The hydroxybenzoic acid compound produced by the
method of the present invention can be used as a raw
material for producing ultraviolet absorber, antioxidant
and the like which are contained in plastics such as
polypropylene.
The present invention is further described in
reference to the following examples. The examples are
intended to illustrate the invention and are not to be
construed to limit the scope of the invention.
432.6 g (2.1 moles)of 2,6-di-tert-butylphenol and
25g (0.3 mole) of 48% aqueous sodium hydroxide were fed in
an autoclave having 1L stainless-steel vessel equipped with
a magnetic stirrer, a thermometer, pressure gauge and
water-separator. The reaction mixture was heated to 210°C
under nitrogen gas flow and at this temperature,
dehydration was conducted for 4 hrs. Next, nitrogen gas in
the vessel was replaced with carbon dioxide gas and
carboxylation was carried out at 210°C under the pressure
of 6 kgf/cm2 (G) with stirring for 2 hrs. After the
reaction was completed, the reaction mixture was cooled to
60°C and 800 g of water was added thereto. The obtained
mixture was heated to 65 °C and the mixture was separated
into the water and solvent phases.
To thus obtained water phase, 73% aqueous
sulfuric acid was added to precipitate crystal and the
crystal was filtrated, washed with water and dried. As a
result, 60g of powdery 3,5-di-tert-butyl-4-hydroxybenzoic
acid was obtained. The yield to the fed amount of sodium
hydroxide was 80%.
To the solvent phase removed from the water phase
in example 1, 51.5 g (0.25 mole) of 2,6-di-tert-butylphenol
and 25g (0.3 mole) of 48% aqueous sodium hydroxide were
added. According to the similar method with example 1,
59.3g powdery 3,5-di-tert-butyl-4-hydroxybenzoic acid was
obtained. The yield to the fed amount of sodium hydroxide
was 79%.
It was confirmed that the solvent phase separated
from the reaction mixture in example 1 did contain little
amount of side-products and could be used again as starting
material of the method of the present invention.
By the same method as Example 1 except that
dehydrating step was conducted at 180°C, 37.5 g of powder
of 3,5-di-tert-butyl-4-hydroxybenzoic acid was obtained.
The yield to the fed amount of sodium hydroxide was 50%.
The same method as Example 1 was carried out
except that dehydrating step was conducted at 150°C. In
the comparative example 1, no precipitation was generated
by adding 73% aqueous sulfuric acid and 3,5-di-tert-butyl-4-hydroxybenzoic
acid could not be obtained.
The same method as Example 1 was carried out
except that 2,4-di-tert-butylphenol was used instead of
2,6-di-tert-butylphenol, 60g of powdery 3,5-di-tert-butyl-2-hydroxybenzoic
acid was obtained. The yield to the fed
amount of sodium hydroxide was 80%.
The present invention provides a method for
producing highly pure hydroxybenzoic acid compound with
high yield and little side-products. The present invention
makes it possible to produce hydroxybenzoic acid compound
by simple steps at low cost without using expensive aprotic
polar organic solvent.
Claims (10)
- A method for producing a hydroxybenzoic acid compound comprising, dehydrating a phenol compound and an alkaline metal compound to form the alkaline metal salt of the phenol compound and reacting the alkaline metal salt and carbon dioxide, wherein the dehydrating step is conducted by reacting the alkaline metal compound with an excess amount of the phenol compound, which is in excess of the alkaline metal compound, at a temperature of 160°C or above.
- The method of claim 1, wherein said dehydrating step is conducted at a temperature of 180-300°C.
- The method of claim 1, wherein 2-30 parts by mole of the phenol compound is reacted per 1 part by mole of the alkaline metal compound.
- The method of claim 1, wherein the phenol compound is a compound represented by formula (I):wherein, R is selected from the group consisting of hydrogen atom, linear or branched chain C1-20 alkyl, C1-20 alkenyl and C1-20 alkoxy groups; n is an integer from 1 to 4.
- The method of claim 1, wherein the phenol compound is an alkyl substituted phenol.
- The method of claim 1, wherein the phenol compound is a di-alkyl substituted phenol.
- The method of claim 5 or 6, wherein, the alkyl group of the alkyl substituted phenol is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl and octyl.
- The method of claim 1, wherein the phenol compound is selected from the group consisting of o-cresol, p-cresol, m-cresol, 2,6-dimethylphenol, 3,5-dimethylphenol, 2,5-dimethylphenol, o-isopropylphenol, 2,6-di-tert-butylphenol, 2,4-di-tert-butylphenol, 2,5-di-tert-butylphenol, 4-n-octylphenol and 4-tert-octylphenol.
- The method of claim 1, wherein the phenol compound is 2,6-di-tert-butylphenol or 2,4-di-tert-butylphenol and said hydroxybenzoic acid is 3,5-di-tert-butyl-4-hydroxybenzoic acid or 3,5-di-tert-butyl-2-hydroxybenzoic acid.
- The method of claim 1, wherein the alkaline metal compound is sodium hydroxide or potassium hydroxide.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002288732A JP2004123592A (en) | 2002-10-01 | 2002-10-01 | Method for producing hydroxybenzoic acid compound |
| JP2002288732 | 2002-10-01 | ||
| PCT/JP2003/012458 WO2004031113A1 (en) | 2002-10-01 | 2003-09-30 | Process for production of hydroxybenzoic acids |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1559705A1 true EP1559705A1 (en) | 2005-08-03 |
| EP1559705A4 EP1559705A4 (en) | 2007-04-25 |
Family
ID=32063689
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP03799169A Pending EP1559705A4 (en) | 2002-10-01 | 2003-09-30 | Process for production of hydroxybenzoic acids |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US20060052632A1 (en) |
| EP (1) | EP1559705A4 (en) |
| JP (1) | JP2004123592A (en) |
| KR (1) | KR20050062574A (en) |
| CN (1) | CN1684935A (en) |
| TW (1) | TW200405891A (en) |
| WO (1) | WO2004031113A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7938902B2 (en) | 2006-09-01 | 2011-05-10 | Buhler Partec Gmbh | Cationically stabilized aqueous silica dispersion, method for its production and its use |
Families Citing this family (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005336121A (en) * | 2004-05-28 | 2005-12-08 | Ueno Seiyaku Oyo Kenkyusho:Kk | METHOD FOR PRODUCING 3,5-DI-tert-BUTYL-4-HYDROXYBENZOIC ACID |
| JP2006315981A (en) * | 2005-05-11 | 2006-11-24 | Ueno Technology:Kk | Method for producing 3,5-di-tert-butyl-4-hydroxybenzoic acid |
| CN101239905B (en) * | 2008-03-19 | 2010-04-14 | 哈尔滨工业大学 | Method for preparing dihydroxy phthalic acid |
| KR101196354B1 (en) * | 2010-09-03 | 2012-11-01 | 서유헌 | Pharmaceutical composition for prevention or treatment of neurodegenerative brain diseases |
| JP5793020B2 (en) * | 2011-08-19 | 2015-10-14 | 本州化学工業株式会社 | Process for producing 2,6-dihydroxybenzoic acid |
| CN102690195B (en) * | 2012-03-06 | 2015-02-18 | 江苏添鑫生物工程有限公司 | Para-hydroxybenzoic acid continuous production technique by liquid-phase method |
| CN102838482B (en) * | 2012-09-20 | 2015-02-04 | 山东潍坊润丰化工股份有限公司 | Preparation method of 3,6-dichlorosalicylic acid |
| CN103012123B (en) * | 2012-12-20 | 2014-11-26 | 浙江大学 | Synthetic method for 3,6-dichloro-2-hydroxybenzoic acid |
| CN103012124B (en) * | 2012-12-26 | 2015-03-25 | 浙江大学 | Preparation method of 3,6-dichloro-2-hydroxybenzoic acid |
| WO2019028600A1 (en) * | 2017-08-07 | 2019-02-14 | Rhodia Operations | Process for production of carboxylated phenol derivatives |
| CN107573236A (en) * | 2017-09-25 | 2018-01-12 | 兰州精细化工高新技术开发公司 | The process for purification of the hydroxybenzoic acid of 3,5 di-t-butyl 4 |
| CN108440273B (en) * | 2018-04-08 | 2021-01-08 | 湘潭大学 | Method and device for preparing o-tolyloxy acetic acid through continuous condensation reaction |
| CN109096099B (en) * | 2018-09-28 | 2021-01-12 | 萧县新秀新材料有限公司 | Production method of 3, 5-di-tert-butyl-4-hydroxybenzoic acid |
| CN109534982A (en) * | 2018-11-22 | 2019-03-29 | 甘肃省化工研究院有限责任公司 | A kind of production method of 3,5- di-tert-butyl-4-hydroxybenzoic acid |
| WO2020179769A1 (en) * | 2019-03-06 | 2020-09-10 | 本州化学工業株式会社 | Production method for 4-hydroxy-2-methyl benzoate |
| US11767281B2 (en) * | 2020-02-06 | 2023-09-26 | Nandkumar Kashinath Chodankar | Manufacturing and purification technology for high purity Propofol |
| CN116082139A (en) * | 2022-12-27 | 2023-05-09 | 甘肃省化工研究院有限责任公司 | Method and device for preparing salicylic acid ultraviolet absorber |
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| US2745882A (en) * | 1953-02-05 | 1956-05-15 | Exxon Research Engineering Co | Dehydrative distillation for preparation of alkali metal salts of 2, 4, 6-trialkylphenols |
| US3816521A (en) * | 1967-10-02 | 1974-06-11 | Ueno Pharm Co Ltd | Process for the production of p-hydroxy benzoic acid |
| US4272635A (en) * | 1979-07-26 | 1981-06-09 | The Dow Chemical Company | Production of alkali metal phenates |
| EP1600435A1 (en) * | 2003-03-04 | 2005-11-30 | Kabushiki Kaisha Ueno Seiyaku Oyo Kenkyujo | Process for production of hydroxybenzoic acids |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS356211B1 (en) * | 1957-10-08 | 1960-06-01 | ||
| JPS61115053A (en) * | 1984-11-09 | 1986-06-02 | Ueno Seiyaku Oyo Kenkyusho:Kk | Production of aromatic hydroxycarboxylic acid |
| US6392090B1 (en) * | 1996-10-02 | 2002-05-21 | Mitsui Chemicals, Inc. | Process for preparing hydroxybenzoic acids |
| JP4093648B2 (en) * | 1998-08-31 | 2008-06-04 | 上野製薬株式会社 | Aromatic hydroxycarboxylic acid production process |
-
2002
- 2002-10-01 JP JP2002288732A patent/JP2004123592A/en active Pending
-
2003
- 2003-09-29 TW TW092126797A patent/TW200405891A/en unknown
- 2003-09-30 KR KR1020057005483A patent/KR20050062574A/en not_active Application Discontinuation
- 2003-09-30 US US10/529,899 patent/US20060052632A1/en not_active Abandoned
- 2003-09-30 WO PCT/JP2003/012458 patent/WO2004031113A1/en active Application Filing
- 2003-09-30 CN CNA038235331A patent/CN1684935A/en active Pending
- 2003-09-30 EP EP03799169A patent/EP1559705A4/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2745882A (en) * | 1953-02-05 | 1956-05-15 | Exxon Research Engineering Co | Dehydrative distillation for preparation of alkali metal salts of 2, 4, 6-trialkylphenols |
| US3816521A (en) * | 1967-10-02 | 1974-06-11 | Ueno Pharm Co Ltd | Process for the production of p-hydroxy benzoic acid |
| US4272635A (en) * | 1979-07-26 | 1981-06-09 | The Dow Chemical Company | Production of alkali metal phenates |
| EP1600435A1 (en) * | 2003-03-04 | 2005-11-30 | Kabushiki Kaisha Ueno Seiyaku Oyo Kenkyujo | Process for production of hydroxybenzoic acids |
Non-Patent Citations (1)
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| See also references of WO2004031113A1 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7938902B2 (en) | 2006-09-01 | 2011-05-10 | Buhler Partec Gmbh | Cationically stabilized aqueous silica dispersion, method for its production and its use |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2004123592A (en) | 2004-04-22 |
| EP1559705A4 (en) | 2007-04-25 |
| KR20050062574A (en) | 2005-06-23 |
| US20060052632A1 (en) | 2006-03-09 |
| TW200405891A (en) | 2004-04-16 |
| WO2004031113A1 (en) | 2004-04-15 |
| CN1684935A (en) | 2005-10-19 |
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